Flavor



United States Patent FLAVOR Irving 1.. Rusolf, Park Ridge, .N.J., assignor tovGeneral Foods Corporation,WhitePlains, N.-Y., acorporation of Delaware No Drawing; ApplicatlonMarch6, 1958. SerialNo. 719,697

15 Claims. (Cli 99-140).

This-invention relates :to artificial .chocolateiflavor and to ayprocessvfor making the same. More particularly, the invention is concerned with an. artificial chocolate flavor component whichmay be used as abaseflavor factor incombination with other. flavor factors such as :astrin gency, bitterness, and the like, or which may be used alone. and without such. other factors to enhance the flavor. of natural chocolate. products. This application relates to the subject matter of my co-pending application; Serial No. 655,200, filed April 26, 1957, now Patent No. 2,835,592, and is thus a continuation-in-part of. that. co-pending. application.

Flavor. derived from. cacao for manufacture of chocolate. and cocoa. productsrinvolvesnumerous Widelyseparated andadistincthsteps commencing; at thev plantations in tropical environs andcontinuinguntil incorporation of theflavor int a finished productswhich canbe a.confectionery, beverage, or like; food product. From the time cacao seeds. are removedfrom their. pods and arersubjected 'to well-known processes which include: fermentation, drying, grading, etc, obscure chemical reactions take-.placethat. condition; the beans forroasting; during which the characteristic flavor of chocolate is developed- While progress has beerrmade in theart of developing. naturahchocolate flavor, the processes involved-.require' a high degree of controlwand are widely' separated,.the flavor: variesnwith the source of the cacao, and the .cost is. excessive.

Theinvention has for-its primary object the eliminationiof reliance. on cacao. as-the sole. source ofchocolate flavor by developmentoftsuchflavor from a widevariety of other raw materials:

It. has been discovered. that partiallyhydrolyzed corn proteinscan be reactedwith reducing sugars andnprecursors thereofato. provide an imitation or artificialchocolate flavor component. which may be: used. as thecbase flavor factor. By base flavor factor ismeans a flavor component which. may be used in. combination with bitterness, astringencyand other flavor factors to. provide an imitation or artificial chocolate. flavor. The base flavor factor may also be employed to enhance theflavor of. natural. chocolate products. The. base flavor. factor provides fullness andborly-whichlevels out and prolongs the taste sensation.-

Thereaction to devclop the. above-described base flavor factor is carried. out by theapplication of heat toa mixture of the reagents; at a temperatureand, fora time suficient to producethe basetflavor-factorin a substantially anhyd-rousrcondition at leastv at the. end ofith'e reaction-.: The reaction is carried out at a temperature of 909-130 Chwherethe saccharide isa pentose; l20l50 C. where thessaccharidei is selected from the. group of hexoseszand reduci g polysaccharides; and l40-170. C. where. the. seccharidev is: a. non-reducing polysaccharide which. is aprecursor.of..a-reducing..saccharide, the time for such reaction .varyinginversely with. temperature. Anyoneofat number of well-knownapparatus maybe employed to carryout thereaction such as a spray drier,

a pan roaster, a drum drier, and the like... Thereaction whichresults in. the productionof the baseflavorcomponentappears. to be accompanied .bya substantial decrease in the measurableamino nitrogen and reducing; sugars in the reaction mixture.

The corn protein degradation techniqueemployed-here! in to produce the: partially hydrolyzed proteinmavbe, enzymatic, acidic, or alkaline, although it is preferred. for the purpose of the present process that enzymatic oracidic hydrolysis be utilized. Of. these cornprotein; hydrolysis methods that which. ismost .preferredis the one employing enzymes. Such enzymes include the pro.- teolytic enzymes such as trypsin,;rennin, pepsin, erepsin,-, papain, bromolin, and the like. The useof alkaline deg: radation of theprotein frequently results in thedevelop-:- ment of undesirable oif-flavors in.,the final product, the: artificial base flavor factor. Both alkaline and aciddee gradation 31'6'111016 difl'lcult. to control as compared with the enzyme degradation require expensive, corrosion-1 prooflequipment and,.moreover, in. some cases destroy certain amino acids. which as set forth hereinafter are desired from the standpoint. of obtaining best results. The degree of hydrolysis or. proteolysis required in the present invention is substantially between 8% and. 70%, viz., 8-70% of the total nitrogen in thehydrolyzateis. amino nitrogen. Generally, it has been found that as the degreeof proteolysis increases, the fiavor intensity of the base flavor factor also increases.

Itis believed that the degree of corn protein hydrolysis employed as described above is such that thepepa tidesnin: the protein. hydrolyzates: are di tri-, andthe; somewhat more complex peptides which can best be de'-: scribed as-oligopeptides. The;termoligopeptidesf is employed herein to denotedi.-,.t1'i-, and up to pentaand hexapeptides, It. has been found that substantially unhydrolyzed proteins on. the one. hand and amino acids on the other hand are incapable ofreaction. with the ,I'fir: ducing sugars to provide the base flavor. factor and that. partially hydrolyzed protein is essential to provide said factor; best results are obtained with oligopeptides. However, some amino. acids t suchas alpha-amino-n-butyric. acid, histidine, alanine, arginine, asparticcacid,glycine; glutamic acid, valine, phenylalanine, proline, lysine, isoleucine, leucine, threonine, tyresine, and tryptophane; when. presentat the time of reacting the oligopeptides with the. reducingsugars result in..a. considerably en-. hanced base flavor factor. Of these. aminov acids, phen. ylalanine and threonine are particularlypreferred.

The above-specified operable rangeof partial hydrolysis for corn proteins, viz., 870, is anexpressionof the percent. hydrolysis within which the corn proteins. tested. have been found to yield the base. flavor factor.

under the reaction conditions of the present invention.

Sorenson and described in the Ofiicial Methods of. Analysis of' the Association of Official. Agricultural.

Chemists, 7th ed., A.O.A.C., Washington, DC. (1950), onpagc 365. Generally, in. the. case of pure. proteins,

formol nitrogen determination by the Greenberg method.

can beconverted to Sorenson values by multiplying the. Greenberg values by the factor 0.56. With proteins. in: a highly buffered system, this conversion factor cannot .be

employed because values provided by the two different methods of analysis do not differ proportionately as they do with pure protein.

' The corn protein hydrolyzate may be reacted with any suitable reducing saccharide, that is, a saccharide capable of reducing Fehlings solution to give cuprous oxide, or with any suitable precursor thereof, which expression includes all saccharides and other materials that provide 'a reducing saccharide or saccharides under the conditions of the reaction. These precursor materials consist mainly of those diand polysaccharides which undergo molecular cleavage to yield reducing saccharides, such as the disaccharide, sucrose; the trisaccharide, rafiinose; the polysaccharide material, dextrin, which of itself comprises both reducing saccharides and precursors thereof;v

etc. The reducing saccharides include all monosaccharides, disaccharides of the gentiobiose type, the trisaccharide manninotriose, etc. In addition, certain saccharic materials can be used which are derived from or closely related to the monosaccharides and have similar reducing properties, such as the -uronic acid, galacturonic acid; the desoxy sugar, rhamnose; and the pentaacetate of galaetose. Thus the term reducing saceharide as used in the claims will be understood to include all of the reducing saccharide and saccharic compounds and precursors which provide reducing saccharide or saccharic compounds under the conditions of the reaction by degradation of the molecule or in any other manner.

Generally, the reducing sugar and the corn protein hydrolyzate may be reacted in widely varying proportions by weight. The amount of reducing sugar may range, for example, from -150% by weight of the protein hydrolyzate and excellent results will be obtained. In the case of monosaccharides like glucose, base flavor factor is obtained in the range of 5-20% glucose by weight of corn protein hydrolyzed to 50%, optimum flavor being derived at levels of glucose between 545%.

The temperature and time of reaction depend on the nature of the reactants, particularly the saccharide. For example, the greater reactivity of the monosaccharides make possible the use of lower temperatures without requiring excessive heating periods, whereas, in the case of less reactive disaccharides it is desirable to employ higher temperatures.

The useful saccharide materials can be divided into the following groups according to the preferred temperature ranges of the reaction, although it will be understood that the stated limits of these preferred ranges are not necessarily the minimum or maximum temperatures at which some useful results can be secured.

(1) The pentoses, including aldopentoses, methyl pentoses, ketopentoses, etc. Examples are xylose, arabinose and rhamnose. For this group, the preferred temperature range of the reaction is from 90 C. to about 130 C.

i (2) The hexoses and reducing polysaccharides. In common with the pentoses of group 1, these reducing saccharides of group 2 have reactive aldehyde or ketone groups which are free to participate directly in the reaction with the protein hydrolyzates, but are less reactive than the pentoses so that the preferred temperature range for the reaction is approximately from 120 C. to 150 C. Examples are the aldohexoses such as glucose, galactose and mannose; the ketohexoses such as levulose and sorbose; reducing disaccharides such as lactose and maltose and other disaccharides of the gentiobiose type; the reducing trisaccharide manninotriose; etc. With this group may also be classified saccharide mixtures such as corn syrup and malt syrup which contain both dextrose and maltose, and invert sugar which contains dextrose and levulose. In addition, such saccharic materials as galacturonic acid and the pentaacetate of galactose can be used in this temperature range.

(3) Non-reducing polysaccharides which are precursors of reducing saccharides, as explained above. In this group, the temperature must be high enough in the first place to cause the formation of the reducing saccharide, and the preferred temperature range is approximately C. to C. Examples are the polysaccharides sucrose, dextrin and raffinose.

As indicated above, the reagents are heated at a temperature and for a time suflieient to create a substantially anhydrous condition at least at the end of the reaction. It appears that the properly mixed reactants require removal of sufficient quantities of water to provide a substantially anhydrous somewhat molten mixture for roasting to develop the artificial chocolate flavor of the present invention. However, the term substantially anhydrous" is not meant to exclude the presence of some water in solution. In fact, a small amount of water is formed continuously during the course of the reaction, which fact alone is sufficient to preclude a completely anhydrous molten state at the end of the reaction. No analytical methods are available which permit determining with accuracy the maximum amount of water permissible at the end of the reaction. Good results have been obtained when the end product at the reaction temperature contained sufiicient moisture to render it more or less tacky in nature, and I believe that as much as 510% moisture may have been present in some of such cases. These figures cannot be determined definitely, however, and in practice it is satisfactory to observe the rule that the product upon cooling to room temperature is substantially solid and substantially dry to the touch. The term substantially anhydrous is to be understood to include the presence of moisture within this limitation.

As aforementioned, the base flavor factor of the present invention can be combined with various other flavor factors of chocolate such as bitterness, astringency, aroma, and like factors in the preparation of an artificial chocolate flavor. The bitterness, astringency, aroma, and like factors, whether employed alone or in combination, fail to provide an artificial chocolate flavor but when one or more of these factors is combined with the base flavor factor of the present invention the taste sensation is leveled ofi? and prolonged because of the fullness and body provided by the base flavor factor. The base flavor factor can be regarded as a background against which the more distinctive flavor factors such as bitterness, astringency, aroma and the like can be better appreciated.

Bitterness may be provided by the addition of bitter alkaloids such as cafrein, theobromine, quinine, and the like. Other bitterness flavor factors that may be employed are the bitter polyacetates of polyhydric compounds such as the monosaccharides, glycose and levulose; the disaccharides, sucrose, lactose andmaltose; the polyhydric alcohols, such as orbitol and mannitol. Included in this class of bitterness factors are sucrose octaacetates, glucose triacetate, glucose tetraacetate, glucose, pentaacetate, levulose triacetate, levulose tetraacetate, levulose pentaacetate, maltose octaacetate, sorbitol hexaacetate. Generally, the beta isomer of the polyacetates is much more bitter than the alpha isomer. Another class of bitterness flavor factors which may be employed are the bitter glucosides, such as quassin, naringin, the alphaphenol-glucoside, beta-phenol-glycoside, 2,3,5,6-tetra-acetyl alpha phenol glycoside, 2,3,5,6 tetra acetylbeta phenol glycoside, 2,3,5,6 tetra acetyl alphamethyl-glucoside, 2,3,5,6-tetra-acetyl-beta-methyl-glucoside. Still another group of bitterness flavor factors are the bitter acetonylated sugars such as diacetone-glucose, 3-acetyl-diacetone-glucose, 3 -acetyl-monoacetone-glucose, 3-benzoyl-diacetone-glucose, and 6-benzoyl-rnonoacetoneglucose. Still another class of bitter flavor factors are salts and esters of inorganic acids such as dulcitol penta nitrate, potassium sulfate, iso-amyl potassium sulfate, methyl-hexylcarbonol potassium sulfate.

Astringency may be provided by employing various tannins or 44?! Obtained by infusion or evaporation assraass;

Otherastringent materials includethe alums suchasso:

dium, potassium, ammonium, and like alums.

Chocolate. aroma materials that can be employed in combination. with the base .flavor factor of the present.

invention, preferably alongwith the .bitterness and as:

tringency flavor factors described above, include aromatic" materials derived from chocolate liquor, cocoa beans, cocoa powder by distillation, solvent extraction, and the like. In order to have a completely artificial chocolate flavor, however, one may employ a mixture of oil of coriander, vanillin, ethyl vanillin, oil of nutmeg, cinnamon and other essential oils which provide an aromatic principle similar to that of natural chocolate.

The base flavor factor resulting from the process of the invention is usually a powdery, friable material which is soluble in aqueous medium such as water, milk, and the like. The product is capable of incorporation into a number of food products, either as the base flavor factor in an artificial chocolate flavor or to enhance the flavor of natural chocolate. The base flavor factor of the present invention alone or with other flavor factors of chocolate can be included in a wide variety of confectionery products such as chocolate bars, candy coatings, cocoa powders for milk drinks and baked goods. Advantageously, the product may be combined with fats such as cocoa butter or with other fats and oils.

The following example illustrates an embodiment of the invention, but it is to be understood that this example is for purposes of illustration and that the invention is not limited thereto, since various changes can be made by those skilled in the art without departing from its scope and spirit.

The following compositions were thoroughly mixed in a 50 cc. beaker:

Reaction ingredients: Percent composition Corn protein (zein) hydrolyzate (20.5% hy- To the above mixture of ingredients 30% water was added until a pasty consistency was obtained. The mixture was then heated for 8 minutes at approximately 130 C. in an oil bath and yielded a dark brown, watersoluble, friable substantially anhydrous mass. 0.5 gm. of the powdered product was dissolved in 100 ml. of whole milk containing grns. of sucrose to provide a chocolate flavored milk drink. Alternatively, the corn protein hydrolyzate and the reducing sugars arabinose, glucose and fructose may be reacted in the oil bath to provide the base flavor factor, the tannins, theobromine and the caflein being added after the reaction to provide the desired artificial chocolate flavor.

The base flavor factor of the present invention may be employed in the enhancement of natural chocolate products such as coatings using, for example, the following procedure. 32 lbs. of chocolate liquor, lbs. of cocoa butter, 45 lbs. of coating sugar, 3.5 lbs. of skim milk powder, and 2 lbs. of .the base flavor factor of. the. present invention as.provided, for example, by the process above, are mixed in aregular chocolate blender heated at. a temperature of 120FQ, saidmixingrequiringabout 20*n1inutes. on the other hand, a melangeur may be employedintplace 'of "the aforementioned blender. The.

blended""materialiisthen "ground in a 5-roll grinder or.

refiner; and-.the liquor is' then conched for about 36*hours after which additional cocoa butter isaddedtoredu'ce.

viscosity ifdesired.

Another unique advantage of the present invention is.

that the. reaction to develop the .base flavor factor may be carrled out using reagents which are found'in corn. Thus, the baseflavor factor can be obtained from a single raw materiakb'y hydrolyzing th'e .corn' protein (with' acid". or enzyme);'.the' saccharide is present in the corn as corn starch, whichcantbe hydrolyzed (e.g., by' acid) to.

give corn syrup having a' substantial dextrose equiva lency; e.g., 24 to'42"D'.E.; the digest can then be reacted at an elevated temperature, preferably between i120- 150 C., and the base flavor factor developed in this manner presents a convenience of operation which offers a substantial economic saving, when large quantities of the base flavor factor are being prepared. However, if it is so desired, the base flavor factor may be prepared by combining the hydrolyzate of the protein with the isolated saccharide.

It will be understood that while the invention has been described in part by means of specific examples, reference should be had to the appended claims for a definition of the scope of the invention.

What is claimed is:

l. A process for producing a chocolate base flavor factor comprising reacting a partially hydrolyzed corn protein with a saccharide by the application of heat to.

reaction, the reaction being carried out at a temperature 1 of 99-l30 C. where the saccharide is a pentose; 120- 150 C. where the saccharide is selected from the group of hexoses and reducing polysaccharides; and 140-l70 C. where the saccharide is a non-reducing polysaccharide which is a precursor of a reducing saccharide.

2. The process of claim 1 in which the protein is hydrolyzed to 870%.

3. The process of claim 1 in which the reducing saccharide is a pentose and the reaction is carried out at a temperature within the range of l30 C.

4. The process of claim 1 in which the reducing saccharide is a polysaccharide and the reaction is carried out at a temperature within the range of -150 C.

5. The process of claim 1 in which the reducing saccharide is a non-reducing polysaccharide which is a precursor of a reducing saccharide formed under the conditions of the reaction and the reaction is carried out at a temperature within the range of l40170 C.

6. The process of claim 1 in which the reducing sugar is corn syrup.

7. An artificial chocolate flavor which comprises in combination the base flavor factor of claim 1 and a bitterness flavor factor.

8. A cacao material of enhanced chocolate flavor which comprises in combination the base flavor factor of claim 1 and chocolate liquor.

9. An artificial cocolate flavor which comprises in combination the base flavor factor of claim 1 and a bitter polyacetate of a polyhydric compound selected from the group consisting of sugars and polyhydric alcohols.

10. The process of claim 1 in which the protein is hydrolyzed to 20-30%.

11. An artificial chocolate flavor which comprises in combination the base flavor factor of claim 1 and an astringent flavor factor.

12. An artificial chocolate flavor which comprises in 7 combination the base flavor factor of claim 1, a bitterriess flavor factor and an astringent flavor factor.

13. The process of claim 1 in which the reaction between the partially hydrolyzed protein and the saccharide is carried out in thepresence of an amino acid selected from the group consisting of alpha-amino-n-butyric acid, histidine, alanine, argim'ne, aspartic acid, glycine, glutamic acid, valine, phenylalanine, proline, lysine, isoleucine, leucine, threonine, tyresine, and tryptophane.

, 14. A process for producing a chocolate base flavor factor from a corn product containing corn protein and a saccharide precursor which comprises hydrolyzing the cornprotein 8-70%, hydrolyzing the saccharide precursor to corn syrup, and reacting a substantially anhydrous mixture of said hydrolyzed corn protein and said corn syrup at a temperature of approximately 120-150 C. to develop the chocolate base flavor factor.

15. The product of the process of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,103,495 Ruckdeschel Dec. 28, 1937 2,364,008 Stuart Nov. 28, 1944 2,414,299 Hall Jan. 14, 1947 2,590,646 Pettibone Mar. 25, 1952 FOREIGN PATENTS 107,367 Great Britain Mar. 18, 1918 OTHER REFERENCES The Chemical Senses, by Moncrieif, Leonard Hill Limited, 17 Stratford Place W. 1, London, 1944, pp. 109, 110, 196 and 239.

The Chemistry and Technology of Food and Food Products, by Jacobs, second edition, Interscience Publishers, Inc., New York, 1951, page 1649.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIUN Patent No, 2,887, 388 May 19, 1959 Irving 1., R'dsoff It is hereby certified that error a of the above numbered ppears in the printed specification Patent should read as patent requiring correction and that the said Letters corrected below.

Solumn 2, line 50, for "8 70 read 8= 7O% 5 column 4, line 53, for "orbitol read sorbzitol column 5, line 7, for "clase" read m class column 6, line 40, for 99-l38 So w 9O =l3O 63., line 66, for "coeolate" read. m chocolate em Signed and sealed this 29th day of September 1959 (SEAL) Attest:

KARL HY. MINE ROBERT C. WATSON Attesting Olficer Commissioner of Patents 

1. A PROCESS FOR PRODUCING A CHOCOLATE BASE FLAVOR FACTOR COMPRISING REACTING A PRATIALLY HYDROLYZED CORN PROTEIN WITH A SACCHARIDE BY THE APPLICATION OF HEAT TO A MIXTURE OF THE REAGENTS AT A TEMPERATURE AND FOR A TIME SUFFICIENT TO PRODUCE SAID BASE FLAVOR FACTOR IN A SUBSTANTIALLY ANHYDROUS CONDITION AT LEAST AT THE END OF THE REACTION, THE REACTION BEING CARRIED OUT A TEMPERATURE OF 99* -130* C. WHERE THE SACCHARIDE IN A PENTOSE; 120* 150* C. WHERE THE SACCHARIDE IS SELECTED FROM THE GROUP OF HEXOSES AND REDUCING POLYSACCHARIDES; AND 140* -170* C. WHERE THE SACCHARIDE IS A NON-REDUCING POLYSACCHARIDE WHICH IS A PRECURSOR OF A REDUCING SACCHARIDE. 